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Synthetic Applications of the Carbonyl Generating Grob Fragmentation

Prantz, Kathrin; Mulzer, Johann

 

Chemical Reviews (Washington, DC, United States)  (2010),  110(6),  3741-3766.

  • 1. Introduction
    • 1.1. History
    • 1.2. General Mechanistic Considerations
  • 2. Carbonyl Generating Grob Fragmentation via Ring Cleavage
    • 2.1. Monosulfated 1,3-Diols
    • 2.2. β-Hydroxy Ketones
    • 2.3. Bromide/Iodide as Leaving Group
    • 2.4. Ammonium as Leaving Group
    • 2.5. Acetals
    • 2.6. 3,4-Epoxy Alcohols as Fragmentation Substrates
    • 2.7. Miscellaneous
  • 3. Carbonyl Generating Grob Fragmentation via Ring Expansions
    • 3.1. Monosulfated 1,3-Diols
    • 3.2. β-Hydroxy Ketones
    • 3.3. Enolate-Induced Grob Fragmentation
    • 3.4. Fragmentation of 3,4-Epoxy Alcohols
    • 3.5. Ammonium Ions as Leaving Group
    • 3.6. Miscellaneous
    • 3.7. Miscellaneous without Electrofugal Carbonyl Groups
  • 4. Decarboxylative Fragmentations
  • 5. Tandem Reactions
    • 5.1. Tandem Aldol−Grob Fragmentation Sequence(124, 125)
    • 5.2. Sequential Semipinacol Rearrangement/Grob Fragmentation of Allylic Alcohols(126)
    • 5.3. Intramolecular Barbier Cyclization/Grob Fragmentation(127)
    • 5.4. Grob Fragmentation/Michael Addition(128)
    • 5.5. Intramolecular Aldol Reaction/Acetalization/Grob Fragmentation(129)
    • 5.6. Intermolecular Aldol Reaction/Acetalization/Grob Fragmentation(130)
    • 5.7. Haller/Bauer-Scission/Grob Fragmentation(133)
    • 5.8. Trapping of Primary Ozonides(134)
    • 5.9. Construction of the Core of Zaragozic Acids
    • 5.10. Grob Fragmentation Followed by a Transannular Ketene [2 + 2] Cycloaddition Reaction(136)
    • 5.11. Grob Fragmentation and Stereocontrolled SmI2-Mediated Cyclization(137, 138)
    • 5.12. Free Radical Fragmentation/Elimination Sequence(139)
  • 6. Fragmentation as Unexpected Side Reaction
    • 6.1. Kempane Diterpenes(141)
    • 6.2. Diels−Alder Adducts of Acetoxy-1,3-dienes and p-Benzoquinone(142)
  • 7. Summary and Conclusions
Johann Mulzer
Institute for Organic Chemistry
University of Vienna

Währingerstraße 38
A-1090 Vienna

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